Basic metal carboxylate complex



United States Patent Int. Cl. Cm 1/24; C101 1/18 U.S. Cl. 25239 14Claims ABSTRACT OF THE DISCLOSURE Basic metal carboxylate complexes areobtained by treating an oil-soluble carboxylic acid with a metal base inthe presence of an acidic gas and an alcoholic promoter. The complexesare useful as detergent additives in fuels, oils, and other organiccompositions and are especially useful in lubricating compositions.

This application is a continuation-in-part of earlier applications Ser.No. 565,407, filed July 15, 1966 now U.S. 3,312,618 and Ser. No.858,603, filed Dec. 10, 1959, which application Ser. No. 858,603 is acontinuation-inpart of earlier application Ser. No. 410,461 filed Feb.15, 1954, now abandoned.

This invention relates to new compositions of matter and methods ofpreparing such compositions. In a more particular sense it relates tonew compositions of matter which contain unusually large amounts ofmetal but which are nevertheless fully oil-soluble. These compositionsare prepared by a new process which is both economical and convenient.

It has been established that in the preparation of a soap or salt of anorganic acid, the use of an excessive amount of a neutralizing agent,such as a metal oxide or hydroxide, results in the formation of a stableproduct which contains an amount of metal in substantial excess of thatwhich is theoretically required to replace the acidic hydrogens of theorganic acid used as the starting material. Such a product may beregarded as a double salt which is indicated by the structure below,

applied to the product obtained by the action of an excess of bariumoxide with an organic sulfonic acid. Alternatively this type of productmay be regarded as a basic salt, indicated by the structure below:

Regardless of whichever of these or any other structures is accepted, ithas been shown that such products are valuable because of their gooddetergent or dispersant qualities and their property of neutralizingundesirable acidic bodies, as for example, in crankcase lubricants. Suchproducts are in fact more effective for many applications than thecorresponding normal salts or soaps.

The processes by which these double salts or basic salts are preparedconsist for the most part merely in mixing and heating an acid or itsnormal salt with an'excessive amount of a metal oxide. The maximumamount of metal which can be incorporated into the product in thismanner is equivalent to about 2.3 times the theoretical amount presentin the normal salt. For the purposes of the present invention the ratioof the total metal in the product to the amount of metal which is in theform of the normal salt of the oil-soluble organic acid will hereinafterbe referred to as the metal ratio.

It will be observed that a metal ratio of 2.3, as conice tained in acomposition which contains a maximum amount of metal as prepared by theprocess described above, cannot be explained either by the double saltor the basic salt type of structure. However, a combination of thesetypes, as follows, can be used to indicate products having metal ratiosas high as 4.0.

It has been discovered that oil-soluble metal-containing compositionscan be prepared which contain substantially more metal than indicated bya metal ratio of 2.3. Such compositions may in fact have metal ratios ashigh as 8.0, 9.0, 20, 30 or more, and it will be appreciated thatneither the basic salt, nor the double salt structure, nor a combinationof these can illustrate such high metal ratios.

There have accordingly been developed two theories as to the structureof such compositions and both serve to account for large amounts ofmetal which are present in an oil-soluble material. The one theorypresumes the formation of a complex which contains within its molecularstructure all of the oil-soluble metal. Various representatives of suchcomplexes are possible and some of these are depicted in U.S. 2,616,905and 2,616,924. The second theory is based on the ability of anoil-soluble metal salt to disperse ordinarily oil-insoluble particlesinto a colloidal dispersion. Such a theory thus explains high metalratio compositions by postulating that the composition is a colloidaldispersion of the metal oxide or hydroxide etc. and that this colloidaldispersion is stabilized by the oilsoluble metal salt.

Such compositions which have high metal ratios, i.e., above 2.3, havebeen prepared by a process which utilizes a so-called promoter materialand a certain amount of water to effect the incorporation of excessmetal into the oil-soluble normal salt. The promoter has heretofore beenselected from among such classes of compounds, as phenols, enols,aci-nitro compounds, low molecular weight organic acids, amides, etc.,each of such types of promoters being characterized by its tautomericnature and:

(a) an ionization constant in water of at least about 1X10 at about 25C.;

(b) a water solubility at 50 C. of at least about 0.0005%; and (c) insaturated aqueous solutions at about 25 C. a pH of less than 7.

It has now been discovered that high metal-containing oil-solublecompositions can be prepared by a process which, under certain anhydrousconditions, makes use of other promoters not believed suitableheretofore. The products are economically available from the process ofthis invention, and are of utility, e.g., as lubricant additives,paint-driers, stabilizers for plastics, emulsifiers, fatsplittingagents, rust-Preventives, and the like.

It is a principal object of this invention to provide an oil-solublemetal-containing organic composition which contains in stable form arelatively large amount of metal.

Another object of this invention is to provide a novel process ofpreparing such compositions.

Further objects of this invention will become apparent in the ensuingdescription thereof.

To the accomplishment of the foregoing and related ends, said inventionthen comprises the features hereinafter fully described and particularlypointed out in the claims, the following description setting forth indetail certain illustrative embodiments of the invention, these beingindicative, however, of but a few of the various ways in which theprinciple of the invention may be employed.

Broadly the process of this invention comprises treating an anhydrousprocess mass consisting essentially of an oil-soluble organic acid, orits oil-soluble metal salt, an organic hydroxy compound, and a basicallyreactlng metal compound, with an inorganic acidic matenal. The organichydroxy compound is one in which the hydroxy group is bonded to anon-benzenoid carbon atom. The product of this process is of unknownstructure. As indicated previously, the presence of the relatively largeamount of metal may be explained by presuming that the product either isan organometallic complex or that it is a stable colloidal dispersion.In view of the uncertainty as to which of these presumptions, if either,is correct, it is preferred to refer to such products in terms of theprocess by which they may be prepared.

More particularly, this invention relates to a process for thepreparation of liquid compositions of matter which contain large amountsof metal and which when admixed with mineral lubricating oil will formclear, filterable masses which comprises:

I. Preparing and mixing a mass in which at 50 C. at least 50% of thecomponents are in the liquid state, and in which mass the activecomponents consist essentially of at least one each of the followingcomponents:

A. An oil-soluble organic acid compound, containing at least 12 carbonatoms in the molecule, selected from the class consisting of aliphaticand cyclic; sulfur acids, carboxylic acids, phosphorus acids, the thioacids of any of the foregoing acids, and the metal salts of any of saidacids;

B. An alcohol having from one to four hydroxyl groups, each of which isbonded to a non-benzenoid carbon atom and having an ionization constantnot greater than 1X l in water at 25 C.;

C. A basically reacting metal compound from which the metal cation isliberated when contacted with an acidic material having an ionizationconstant of at least 1.5 in water at 25 C. and present in an amount suchthat there is present in the mass substantially more than one equivalentof metal per equivalent of A;

II. Treating the mass with substantial amounts of at least one inorganicacid material of which the ionization constant is at least 1.5 10 inwater at 25 C.; and the process characterized further in that I (a) thereaction mass, when treated with said 11'1- organic acidic materialcontains substantially no free water; and

(b) if water is liberated during such treatment step as by the use of ametal hydrate as component B, the temperature and other conditions ofreaction are such that substantially all of such liberated water isdriven olf as it is formed.

Still more particularly, this invention relates to a process forpreparing an oil-soluble highly basic metal salt of an organic acid,said process comprising reacting, as the only chemically reactiveorganic material, an oilsoluble organic acid compound selected from theclass consisting of 1) cyclic sulfur acids containing at least 18 carbonatoms per molecule, (2) cyclic carboxylic acids containing at least 17carbon atoms per molecule and (3) salts of those acids with alkalimetals and with alkaline earth metals, in the presence of at least 5% ofthe weight of said organic acid compound of a lower alkanol, with analkaline earth metal carbonate formed in situ, by the reaction of carbondioxide and an alkaline earth metal base, at least a part of said basebeing in the free state, thereafter removing said alkanol and any waterpresent in the resulting mixture. Preferably the oil-soluble organicacid compound is in solution in a hydrocarbon oil.

As indicated previously, the products of this invention have relativelyhigh metal contents and these are reflected by observed metal ratios of7.0, 20, 30 or more. The products are permanently soluble in manyorganic environments and consequently find many applicants, particularlyas additives in the lubricant field.

4 OIL- SOLUBLE ORGANIC COMPOUND STARTING MATERIAL The oil-solubleorganic compound which is one of the starting materials used in theprocess of this invention comprises at least one compound selected fromthe class consisting of oil-soluble organic acids and metal saltsthereof. It may be, for example, a sulfur acid, a carboxylic acid, aphosphorus acid, a thio acid corresponding to any of the foregoingacids, or a metal salt of any of these acids. Similarly mixtures of (a)two or more acids, (b) two or more salts, and (c) at least one acid withat least one salt may be used. The acids preferred for the purposes ofthe present invention contain at least 12 carbon atoms in the molecule.

Specific examples of sulfur acids and their thio analogs includesulfonic, sulfamic, sulfinic, sulfenic, thiosulfonic acids, etc. and ofthese the sulfonic acids have been found to be of particular usefulnessin the ordinary practice of this invention. Among the sulfonic acids arethe following: mahogany sulfonic acid; petrolatum sulfonic acids;monoand polywax substituted naphthalene sulfonic, phenol sulfonic,diphenyl ether sulfonic, diphenyl ether disulfonic, naphthalenedisulfide sulfonic, naphthalene disulfide disulfonic, diphenyl aminedisulfonic, diphenyl amine sulfonic, thiophene sulfonic,alpha-chloro-naphthalene sulfonic acids, etc.; other substitutedsulfonic acids such as cetyl chloro-benzene sulfonic acids, cetylphenolsulfonic acids, cetyl-phenol disulfied sulfonic acids, cetyl-phenolmono-sulfied sulfonic acids, cetoxy caprylbenzene sulfonic acids,di-cetyl thianthrene sulfonic acids, di-lauryl beta-naphthol sulfonicacids, and di-capryl nitronaphthalene sulfonic acids;- aliphaticsulfonic acids such as parafiin wax sulfonic acids, unsaturated parafiinwax sulfonic acids, hydroxy substituted parafiin wax sulfonic acids,tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids,chloro-substituted parafiin wax subacids, nitroso paraffin wax sulfonicacids, etc.; cycloaliphatic sulfonic acids, such as petroleum naphthenesulfonic acids, cetyl-cyclopentyl sulfonic acids, laurylcyclohexylsulfonic acids, bis-(diisobutyl)-cyclohexyl sulfonic acids, monoandpoly-wax substituted cyclohexyl sulfonic acids, etc.

With respect to the sulfonic acids, it is intended herein to employ theterm petroleum sulfonic acids to cover all sulfonic acids which arederived from petroleum products. Additional examples of sulfonic acidsand/or alkaline earth metal salts thereof which can be employed asstarting materials are disclosed in the following US. Patents:2,174,110; 2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,791;2,212,786; 2,213,360; 2,228,598; 2,233,676; 2,239,974; 2,263,312;2,276,090; 2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568;2,333,788; 2,335,259; 2,337,552; 2,346,568; 2,366,027; 2,374,193; and2,383,319.

The carboxylic acids include acyclic fatty acids wherein there arepresent at least about 12 carbon atoms, usually up to about 30 carbonatoms, such as, for example, palmitic, stearic, mlyristic, oleic,linoleic, dodecanoic, behenic, triacontanoic, docosanoic, etc. acids.The acyclic carboxylic acids of the aliphatc type may be saturated orunsaturated and can contain elements in the aliphatic radical other thancarbon and hydrogen; examples of such acids are the carbamic acidsricinoleic acids, chlorostearic acids, nitro-lauric acids, etc. Inaddition to the aliphatic carboxylic acids, it is intended to employ thecyclic types such as those containing a benzenoid structure, i.e.,benzene, naphthalene, etc., and an oil-solubilizing radical or radicalshaving a total of at least about 15 to 18 carbon atoms, preferably fromabout 15 to about 200 carbon atoms. Such acids are the oil-solublealiphatic substituted aromatic acids as for example, stearyl-benzoicacids, monoor polywax substituted benzoic or naphthoic acids wherein thewax group contains at least about 18 carbon atoms, cetyl hydroxybenzoicacids, etc. The cyclic type of carboxylic acids also includes thoseacids which have present in the compound a cycle-aliphatic group.Examples of such acids are petroleum naphthenic acids, cetyl cyclohexanecarboxylic acids, di lauryl deca hydronaphthalene carboxylic acids,di-octyl cyclopentane carboxylic acids, etc. It is also contemplated toemploy the thiocarboxylic acids, that is, those carboxylic acids inwhich one or both of the oxygen atoms of the carboxyl group are replacedby sulfur.

The phosphorus acids include triand pentavalent organic phosphorus acidsand the corresponding thio-acids, which are, for example, phosphorous,phosphoric, thiophosphoric, thiophosphorous, phosphinic, phosphonic,thiophosphinic, thiophosphonic, etc. acids. Among the most useful of thephosphorous acids are those represented by the following formulae:

wherein X and X are either oxygen or sulfur and at least one X and one Xis sulfur, and R and R are each either the same or different organicradicals or hydrogen, and wherein at least one is an organic radical andat least one IR is hydrogen and wherein at least one R is an organicradical and at least R is hydrogen. Therefore, such formulae include theoil-soluble organic thioacids of phosphrous, more particularly, theorganic thiophosphoric acids and the organic thiophosphorus acids. Theorganic radicals R and R can be aliphatic, cycloaliphatic, aromatic,aliphaticand cycloaliphatic-substituted aromatic, etc. The organicradicals R and R preferably contain a total of at least about 12 carbonatoms, preferably up to about 200 carbon atoms, in each of the abovethio-acid types I and II. Examples of such acids are dicapryldithiophosphoric acids, di-(methyl-cyclohexyl) dithiophosphoric acids,dilauryl dithiophosphoric acids, dicapryl dithiophosphorous acids, di-(methyl-cyclohexyl) dithiophosphorous acids, lauryl monothiophosphoricacids, di-(butyl-phenyl)dithiophosphoric acids, and mixtures of two ormore of the foregoing acids.

Certain of the above described thio-acids of phosphorus such as, forexample, di-capryl dithiophosphoric acid are also commonly referred toas acid esters.

A particularly useful type of phosphorus acid may be prepared by thereaction of phosphorus sulfides or chlorides with hydrocarbons having atleast 12 aliphatic carbon atoms. One such acid is prepared from apolyisobutylene by treating it with phosphorus pentasulfide or withphosphorus pentasulfide and sulfur, then with steam. The resultantacidic product contains both phos phorus and sulfur. Another such acidis available from the reaction of a polyolefin such as polypropylenewith thiophosphoryl chloride, followed by treatment with water. Stillanother such acid may be prepared by an aluminum chloride catalyzedreaction of a polyolefin with phosphorus trichloride followed likewiseby steam treatment. Other phosphorus sulfides useful herein includephosphorus heptasulfide, phosphorus sesquisulfide, thiophosphoricchloride, and phosphoric oxysulfide. Polyolefins useful for this purposeoften have molecular weights of from about 150 to about 5000 or up toabout 100,000 or even higher. Many other similar reactions will yieldphosphorous-containing acids which are highly satisfactory for use inthe process described herein.

Products of wide utility in the preparation of improved lubricants canbe made according to our process when using as the oil-soluble organicacid compound starting material a mixture of (l) sulfonic acid and atleast one of the above described phosphorus acids, or (2) the salts ofsaid acids. As will be noted from several of the examples which follow,one method of carrying out the process of this invention depends uponthe in situ formation of the metal salt of the organic acid compound.Thus, instead of using the metal salt of such metal organic compounddirectly in the process mixture, the oil-soluble organic acid can bemixed with an alcohol and a stoichiometrically excessive amount ofalkaline earth metal base and then treated with carbon dioxide asindicated above. This embodiment of the invention is illustrated by thetreatment with carbon dioxide of a mixture of naphthenic acid, a loweralkanol and an alkaline earth metal base in the proportions and underthe conditions set forth earlier herein, and also by Examples 25, 30, 37and 41.

As indicated by the examples cited hereinabove the oil-soluble organiccompound may be either aromatic, aliphatic, cycloaliphatic,arylaliphatic, etc., just so long as it is an oil-soluble acid or anoil-soluble metal salt of an acid.

ORGANIC HYDROXY COMPOUND STARTING MATERIAL The broad class of compoundsuseful as this reagent may be represented by the formula wherein Q is asubstituted or unsubstituted cyclic or acylic organic radical having atleast one non-benzenoid carbon atom; n is an integer of from 1 to 6,preferably, 1 to 4 or 1 to 3, and most desirably l; and OH is bonded toa non-benezoid carbon atom in Q; said compound Q(OH) having anionization constant not greater than 1x 10- in water at 25 C.

The above formula includes, as its most numerous class, the variousmonohydric and polyhydric alcohols, of which the monohydric alcohols arepreferred. While excellent results are obtained, as shown hereinafter,with unsubstituted monohydric alcohols; i.e., alcohols containing onlycarbon, hydrogen, and hydroxyl oxygen, for some purposes, as for exampleuse of the end-products of the invention in lubricants, it is oftendesirable to employ an alcohol which contains at least one substituentgroup such as; e.g. halogen, amino, sulfide, disulfide, ether, etc.

Best results are usually obtained with monohydric alcohols which do notcontain a homocyclic benzenoid ring structure and which have a molecularweight less than 150.

Illustrative of the various Q(OH) compounds which may be used inaccordance with the invention are: unsubstituted aliphatic monohydricalcohols; e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,isobutyl, tertiary-butyl, amyl, n-hexyl, 4-methyl-pentyl-2, heptyl,n-octyl, capryl, n-nonyl, isononyl, Z-ethyl-hexyl, decyl, lauryl, andtetradecyl alcohols; substituted aliphatic monohydric alcohols; e.g.chloro-hexyl, bromo-octyl, fluorodecyl, amino-ethyl, methoxyethoxyethyl,and methylmercapto-ethyl alcohols; unsubstituted cycloaliphaticmonohydric alcohols; e.g. cyclohexyl, methyl-cyclohexyl,propylcyclohexyl, amyl-cyclohexyl, octyl-cyclohexyl, tetrahydrofurfuryl,and decahydronaphthyl alcohols; substituted cycloaliphatic monohydricalcohols; e.g. 2-chloro-cyclohexyl and chlorinated methyl-cyclohexylalcohols; aromatic-substituted aliphatic monohydric alcohols; e.g.benzyl, p-chlorobenzyl, p-aminobenzyl, phenethyl, p-chlorophenethyl, andfurfuryl alcohols; cycloaliphatic-substituted aliphatic monohydricalcohols; e.g. cyclohexylmethyl, cyclohexyl-ethyl, andmethylcyclohexyl-ethyl alcohols; and the various polyhydric alcoholswhich contain from 2 to 6 hydroxyl groups; e.g., ethylene glycol,propylene glycol, quercitol, inositol, sucrose, mannose, sorbitol,butylene-glycol, glyserol, cyclohexandiol-l,4, pentaerythritol, and thelike.

It is also within the scope of the present invention to use mixtures oftwo or more Q(OH) compounds. Particularly useful in some instances arecombinations of a low-boiling alcohol, such as methanol, with ahighboiling alcohol, such as isononyl alcohol.

BASIC METAL COMPOUNDS These compounds are basically reacting metalcompounds from which the metal cation is liberated when contacted wtihan acidic material having an ionization constant of at least 1.5 10- inwater at 25 C. Such compounds include those of alkali and alkaline earthmetals such as sodium, potassium, lithium, magnesium, strontium, barium,and calcium. These compounds are present in an amount such that there ispresent in the mass substantially more than one equivalent of metal perequivalent of oil-soluble organic acid compound.

Oxides and hydroxides comprise the principal and most usefulconstituents of this group; others are the sulfides, hydrosulfides,amides, alcoholates derived from alcohols having, for example, from 1 toabout 30 carbon atoms, etc. Specific examples of the most useful basicmetal compounds include barium oxide, barium hydroxide, lithium oxide,lithium hydroxide, sodium hydroxide, alcoholates, such as bariummethoxide, calcium ethoxide, strontium isopropoxide, etc. The basicinorganic metal compounds are preferred because of their cheapness andavailability.

THE INORGANIC ACIDIC MATERIAL As previously indicated, the presentinvention includes the treatment of the mass with an inorganic acidicmaterial having an ionization constant greater than the organic hydroxycompound. This treatment results in the liberation of at least a portionof the organic hydroxy compound. A particularly effective inorganicacidic material which has been utilized for this purpose is carbondioxide.

It is an important feature or characteristic of the inorganic acidmaterial that it must possess an ionization constant higher than theorganic hydroxy compound. Thus, in the present invention the acidicmaterial must have an ionization constant greater than 1X10 in water at25 C. The inorganic acidic material can be a liquid, gas, or solid priorto being incorporated into the mass. However, the acidic material isusually employed as a liquid or a gas. Liquids can include strong orweak acids, such as, for example, hydrochloric, sulfuric, nitric,carbonic acids, etc., whereas the gas is for the most part an anhydrideof an acid or an acid anhydride gas.

The following are additional specific examples of acidic materials, viz:HCl, S S0 CO air (considered acidic because of CO content) N0 H 5, N 0PCl C H286, S0012, BF3, CS2, I'I2C1O4, etc.

It is to be understood, however, that all acidic materials are notequivalent for the purposes of the present invention, but that undercertain conditions some are more eifective or desirable than others.Special preference is given to carbon dioxide.

A substantial amount of acidic material must be em ployed in theprocess, generally, enough to substantially reduce the titratablebasicity of the mass, and usually in amount sufficient to substantiallyneutralize the mass. Amounts in excess of that required to substantiallyneutralize the mass may, of course, be used. Such stoichiometric excess,however, does not alter the basic characteristics of the process,although in some instances it is a commercial expedient to facilitate anefiicient utilization of the other ingredients of the process mixture.In some cases, however, where the acidic material employed is carbondioxide and the basically reacting metal compound is an alkaline earthmetal base it is preferred that the amount of carbon dioxide reactant isless than the amount theoretically required to convert the free alkalineearth metal base to the corresponding alkaline earth metal carbonate.This embodiment of the invention is illustrated by Examples 5, 7, l5,16, 30, 35 and 41.

8 PROCESS CONDITIONS The organic metal compositions of this inventionmay be prepared by mixing an oil-soluble organic acid or its oil-solublesalt with an Q(OH) compound, and a basic metal compound and introducingthe inorganic acidic material such as carbon dioxide into the processmass. For example, the oil-soluble organic acid (or salt), the Q(OH)compound, and the basic metal compound may be mixed, then treated withgaseous carbon dioxide. Alternatively the basic inorganic metal compoundmay be added portionwise to a mixture of the first two ingredientsmentioned above, while carbon dioxide is bubbled into the reactionmixture.

The amount of alcohol which is to be used in the process is not criticaland it is necessary only that an appreciable amount be used. Thus, foreach equivalent weight of basic, inorganic barium compound which isused, at least 0.1 equivalent weight of alcohol will usually beemployed. Preferably, the amount of alcohol will be 0.25 equivalent ormore, on the same basis. As indicated earlier this minimum amount ofalcohol may also be expressed as at least 5% of the weight of theorganic acid compound used in the process.

The process mass must be substantially anhydrous, that is, containsubstantially no free water, during the step in which the mass istreated with the inorganic acidic material. If water is liberated duringsuch step, as by the use of metal hydrate of the basically reactingmetal compound, the temperature and other conditions of reaction shouldbe such that substantially all of such liberated water is driven off asit is formed.

The addition of the basic inorganic metal compound to a mixture ofoil-soluble organic acid (or salt) and Q(OH) compound results in theevolution of heat. Likewise, the addition of the inorganic acidicmaterial to this mass is an exothermic reaction and it liberates heat.Thus, a typical reaction requires the application of little or no heat,although in some cases it may be advisable to provide some externalheating. A wide range of temperature is permissible, ranging from roomtemperature or even lower, up to about 200 C.

A preferred process involves the simultaneous portionwise addition ofbasic inorganic metal compound and carbon dioxide to a mixture ofoil-soluble acid (or salt) and aliphatic alcohol. The temperature ofsuch a reaction is conveniently that of the refluxing mixture, which inturn is determined principally by the boiling point of the Q(OH)compound employed.

In some instances, however, it may not be convenient to effect theportionwise addition of a solid reagent (the basic metal compound) andin such instances it is preferable first to mix the oil-soluble acid (orsalt), Q(OH) compound, and basic metal compound, and then to bubble incarbon dioxide or add the inorganic acidic material. The mixture may beheated prior to the inorganic acidic material treatment, and likewise itmay be desirable to heat the mixture during the inorganic acidicmaterial treatment.

An essential feature of the process of this invention is that there mustbe present simultaneously in the reaction mass, inorganic acidicmaterial and a basic metal compound. This combination is necessary forthe success of the process and without it, e.g., carbonation completedbefore addition of the basic metal compound, the products of thisprocess cannot be prepared. Obviously there must also be present in thereaction mass an oil-soluble acid (or salt) and Q(OH) compound.

The product which results from any of the above described methods ofprocessing may be further treated so as to remove volatile materials.Such materials will inelude principally the Q(OH),, compound, and theymay be removed by distillation, either at atmospheric pressure orreduced pressure. The ordinary practice of the invention involvesdistillating at atmospheric pressure until no more will distill and thenremoving the last traces of volatile matter by heating the mixture underreduced pressure.

The following examples will illustrate the process in greater detail.These examples are illustrative only and should not be construed aslimiting the scope of the invention. Example 1 shows the inoperabilityof the process when no carbon dioxide was present in the reactionmixture. The other examples all illustrate the process of thisinvention.

The 40 percent barium petroleum sulfonate employed in many of theexamples refers to a 40 percent by weight oil solution of bariummahogany sulfonates. The term Neut. No. refers to the neutralizationvalue as determined by ASTM Test No. D-974-48T.

Example 1 A mixture of 1110 grams (1.0 equivalent) of 40 percent bariumpetroleum sulfonate, 470 grams of mineral oil, 256 grams (8.0equivalents) of methanol and 306 grams (4.0 equivalents) of barium oxidewas heated with stirring at reflux temperature for one hour. At thispoint the mixture had become quite viscous and efforts to reduce thisviscosity by heating, treatment with nonyl alcohol, water, etc., wereunsuccessful.

Example 2 Sulfate ash, percent 33.2

Neut. No. slightly acid Metal ratio 4 7 Example 3 A solution of 1285grams (1.0 equivalent) of 40 percent barium petroleum sulfon-ate in 420grams (7.0 equivalents) of isopropyl alcohol was treated at 6570 C. with301 grams (3.9 equivalents) of barium oxide. The resulting mixture wasstirred for one hour at 8590 C., then treated with carbon dioxide fornine hours, and filtered through hyflo. The filtrate was clear andshowed the following analyses:

Sulfate ash, percent 23.4

Neut. No. (basic) 2 Metal ratio 3.0

Example 4 A solution of 1285 grams (1.0 equivalent) of 40 percent bariumpetroleum sulfonate in 420 grams (7.0 equivalents) of n-propyl alcoholwas treated at 60-100 C. with stirring with 301 grams of barium oxide.The mixture was heated at reflux temperature for one hour, then treatedat this same temperature for two hours with carbon dioxide. Afer thefirst hour of carbon dioxidetreatment the reaction mass had become quiteviscous, but half an hour later it was very fluid. The resulting mixturewas concentrated by heating to 125 C./ 18 mm., then filtered throughhyfio. The clear, brown filtrate showed the following analyses:

Example 5 Sulfate ash 32.1

Neut. No. (basic) 3.6

Metal ratio 4.5

Example 6 A mixture of 1285 grams (1.0 equivalent of 40 percent bariumpetroleum sulfonate, 408 grams (4.0

equivalents) of 2-methylpentanol-4, and 301 grams (3.9 equivalents) ofbarium oxide was heated to 165 C. over a period of one hour and thenheld at ISO-160 C., for an additional hour. Carbon dioxide was bubbledthrough the mixture for four and one half hours at this temperature, andthe resulting mixture was filtered through hyflo. The filtrate was adark brown oil having the following analyses:

Sulfate ash, percent 27.2

Neut. No. (acidic) 0.5

Metal ratio 3.6

Example 7 A mixture of 1533 grams (15.0 equivalents) of 2- methylpentanol-4, 301 grams (3.9 equivalents) of barium oxide, and 1285 grams(1.0 equivalent) of 40 percent barium petroleum sulfonate was heated toC. over a period of one hour and held at reflux temperature for anadditional hour. Carbon dioxide was bubbled through the mixture for 2.5hours at 150 C. then the mixture was concentrated by heating to C./20mm., and filtered through hyflo. The filtrate was a dark brown liquidhaving the following analyses:

Sulfate ash, percent 24. Neut. No. (basic) 2. Metal ratio 3 i oorExample 8 To a solution of 1285 grams (1.0 equivalent) of 40 percentbarium petroleum sulfonate in 714 grams (7.0 equivalents) of n-hexylalcohol there was added with stirring at 75 C., 301 grams (3.9equivalents) of barium oxide. The resulting mixture was heated at 150 C.for one hour, then treated at 140-145 C. with carbon dioxide for twohours. This mixture was concentrated by heating to 150 C./20 mm.Filtration of the residue through hyflo yielded a liquid having thefollowing analyses:

Sulfate ash, percent 27.2

Neut. No. (basic) 0.5

Metal ratio 3.8

Example 9 A mixture 'of 301 grams (3.9 equivalents) of barium oxide,1285 grams (1.0 equivalent) of 40 percent barium petroleum sulfonate and1010 grams (7.0 equivalents) of nonyl alcohol was heated over a periodof two hours to 200 C., then heated with continued stirring at 205-210C. for an additional hour. Carbon dioxide was bubbled into the hot (-205C.) mixture for two hours, and then the mixture was concentrated byheating to 200 C./

18 mm. The residue Was filtered through hyflo to yield as filtrate aclear, brown oil having the following analyses:

Example A solution of 1928 grams (1.5 equivalents) of 40 percent bariumpetroleum sulfonate in 1004 grams of oil and 188 ml. (4.7 equivalents)of methanol was prepared was prepared and heated to 40 C. Carbon dioxidewas bub bled into this solution and 796 grams (10.4 equivalents) ofbarium oxide was added portionwise over a period of two hours. Thetemperature was maintained between 40 C. and 70 C. throughout and whenall the barium oxide had been added the carbon dioxide-treatment wascontinued for an additional four hours. The resulting mixture then washeated to 150 C. and held at this temperature for 30 minutes to removeany volatile material. The residue was filtered through hyflo yielding aclear, brown filtrate, having the following analyses:

Sulfate ash, percent 32.6

Neut. No. (basic) 1.2

Metal ratio 7.2

Example 11 Sulfate ash, percent 15.7 Neut. No. nil Metal ratio 2.9

Calcium, percent 1.0

Example 12 A mixture of 671 grams (1.0 equivalent) of 60 percent sodiumpetroleum sulfonate, 464 grams of mineral oil, and 100 grams of methanol(3.0 equivalents) was stirred at 4055 C. while carbon dioxide was beingbubbled into the mixture and 237 grams (3.1 equivalents) of barium oxidewas being added portionwise over a period of one hour. The carbondioxide-treatment was continued for an additional 1.5 hours at 65-70 C.and then the mixture was freed of volatile materials by heating at 150C. for 30 minutes. The dried mixture was filtered through hyflo,yielding a brown filtrate, having the following analyses:

Sulfate ash, percent 29.0 Neut. No. slightly basic Metal ratio 3.9

Sodium, percent 1.6

It will be noted in the above example that the in situ formation ofbarium sulfonate is accomplished.

Example 13 Sulfate ash, percent Neut. No. (basic) Metal ratio 1 2Example 14 A mixture of 575 grams (0.5 equivalent) of bariumpolydodecylbenzene sulfonate, 153 grams (2.0 equivalents) of bariumoxide, 288 grams of nonyl alcohol (2.0 equivalents) and grams of mineraloil was heated at -160 C. while carbon dioxide was bubbled in until themixture was substantially neutral. The resulting mixture was filteredthrough hyflo. The filtrate showed the following analyses:

Sulfate ash, percent 15.1

Neut. No. (acidic) 2.0

Metal ratio 2.8

Example 15 hour, and filtered through hyflo. The filtrate was a brown,

non-viscous liquid, having the following analyses:

Sulfate ash, percent 12.7

Neut. No. (basic) 3.4

Metal ratio 2.5

Example 16 To a mixture of 555 grams (0.5 equivalent) of 40 percentbarium petroleum sulfonate, 31 grams of ethylene glycol (1.0 equivalent)and 416 grams of mineral oil there was added with stirring at 103-112C., 154 grams (2.0 equivalents) of barium oxide. Ten minutes wasrequired for the portionwise addition, after which the mixture washeated at 178 C. for an hour. The mixture then was treated with carbondioxide at 150 C. for one hour and finally heated at 150-170 C. atreduced pressure for an additional hour. The mixture was filteredthrough hyflo, yielding as filtrate a brown, non-viscous liquid havingthe following analyses:

Sulfate ash, percent 19.6 Neut. No. (basic) 12.2 Metal ratio 3.9

Example 17 To a stirred mixture of 555 grams (0.5 equivalent) of 40percent barium petroleum sulfonate, 108 grams (1.0 equivalent) of benzylalcohol and 416 grams of mineral oil, there was added at 105-120 C., 154grams (2.0 moles) of barium oxide. The addition was made portionwiseover a period of ten minutes. The mixture was heated gradually to 150 C.and held at 150-160" C. for an hour. Carbon dioxide was bubbled into thehot (153- 162 C.) mixture for an hour and the resultant product washeated at 150 C. at reduced pressure for another hour. Filtration ofthis material through hyflo yielded a clear, brown, non-viscous liquidwhich had the following analyses:

Sulfate ash, percent 19.8 Neut. No. slightly basic Metal ratio 4.0

Example 18 13 dioxide. The mixture was heated at 150 C. at reducedpressure to remove volatile materials and then was filtered throughhyflo. The clear, brown, non-viscous filtrate showed the followinganalyses:

Sulfate ash, percent 13.9

Neut. No. slightly acid Metal ratio 2.9

Example 19 A mixture of 555 grams (0.5 equivalent) of 40 percent bariumpetroleum sulfonate, 98 grams (1.0 equivalent) of furfuryl alcohol and416 grams of mineral oil was heated at 103-120" C. while 154 grams (2.0equivalents) of barium oxide was added over a period of ten minutes.This mixture was heated slowly to 150 C. and held at that approximatetemperature for an hour. Carbon dioxide was bubbled into the mixture atthis temperature for an hour, and then all volatile materials wereremoved by heating for an hour at 150 C. at diminished pressure.Filtration of this product through hyflo yielded a clear, brown,non-viscous, liquid having the following analyses:

Example 20 A mixture of 555 grams (0.5 equivalent) of 40 percent bariumpetroleumsulfonate, 177 'grams (1.0 equivalent) of dichlorobenzylalcohol, and 416 grams of mineral oil was heated at 100 C. while 154grams (2.0 equivalents) of barium oxide was added portionwise over aperiod of ten minutes. The temperature was raised slowly to 150 C. andheld thereafter at 150-170" C. for an hour. Then carbon dioxide wasbubbled into the mixture at 150 C. for 1.5 hours. Volatile materialswere removed by heating for an hour at ISO-165 C. at reduced pressure.Filtration through hyflo yielded a brown, non-viscous liquid, having thefollowing analyses:

A mixture of 278 grams (0.25 equivalent) of 40 percent barium petroleumsulfonate, 122 grams-(0.8 equivalent) of monochlorinatedmethyl-cyclohexanol, and 208 grams of mineral oil was heated at 100 C.while 77 grams (1.0 equivalent) of barium oxide was added portionwiseover a ten-minute period. The temperature was raised slowly to 150 C.and held there for 30 minutes. Carbon dioxide was bubbled into the hot(ISO-158 C.) mixture for an hour. The resultant mixture was freed ofvolatile matter by heating for an hour at ISO-187 C. at reducedpressure. Filtration of the residue through hyflo yielded as filtrate aclear, brown, non-viscous liquid which had the following analyses:

Sulfate ash, percent 19.4

Neut. No. (acidic) 3.9

Metal ratio 4.1

Example 22 14 was filtered through hyflo. The filtrate was a clear, darkbrown, non-viscous liquid having the following analyses:

A stirred mixture of 57 grams (0.4 equivalent) of nonyl alcohol and 301grams (3.9 equivalents) of barium oxide was heated at 150-175 C. for anhour, then cooled to C. whereupon 400 grams (12.5 equivalents) ofmethanol was added. The resultant mixture was stirred at 70-75 C. for 30minutes, then treated with 1285 grams (1.0 equivalent) of 40 per-centbarium petroleum sulfonate. This mixture was stirred at refluxtemperature for an hour, then treated with carbon dioxide at -6070 C.for two hours. The mixture then was heated to 160 C./l8 mm. and filteredthrough hyflo. The filtrate was a clear, brown oil having the followinganalyses:

A stirred solution of 1285 grams 1.0 equivalent) of 40 percent bariumpetroleum sulfonate, 408 grams (4.0 equivalents) of 2-methyl pentanol-4,and 400 grams (12.5 equivalents) of methanol was maintained at 4058 C.while 301 grams (3.9 equivalents) of barium oxide was added portionwiseover a period of one hour. The mixture was stirred for an hour at 60-70C., then treated with carbon dioxide at the same temperature for twohours. Volatile materials were removed by heating the reaction mass to150 C./ 17 mm. and the residue was filtered through hyflo. The filtratewas a clear, brown oil having the following analyses:

Example 25 To a stirred mixture of 795 grams (0.5 equivalent) of thebarium salt of a phosphorus-and sulfur-containing acid (prepared bytreating a polyisobutylene with phosphorus pentasulfide and sulfur, thenwith steam) and 643 grams (0.5 equivalent) of 40 percent bariumpetroleum sulfonate there was added at 40 C., 306 grams (4.0equivalents) of barium oxide. Carbon dioxide then was bubbled into themixture while grams (3.1 equivalents) of methanol was added portionwiseover a period of 1.5 hours at 40-60 C. The carbon dioxide treatment wascontinued for an additional 3.5 hours at 60-70 C. The mixture was freedof volatile materials by heating to C., then it was filtered. Thefiltrate was a clear, brown, viscous oil having the following analyses:

Example 26 A 516-gram sample (0.67 equivalent) of a phosporousandsulfur-containing acid (prepared by treating a polyisobutylene withthiophosphoryl chloride, then with steam) was mixed with 102 grams ofmineral oil and 42.8 grams (1.3 equivalents) of methanol and heated to35 C.; 51.2 grams (0.67 equivalent) of barium oxide was added and theresultant mixture was stirred at reflux temperature for an hour. Anadditional 106.5 grams (1.41 equivalents) of barium oxide then was addedportionwise throughout the next 45 minutes at 35-55 C. and while carbondioxide was being bubbled into the mixture; the carbon dioxide treatmentwas continued for an additional two hours at 5560 C., whereupon themixture was heated to 150 C. then filtered through hy- Ho. The filtratehad the following analyses:

A mitxure of 83.5 grams (0.25 equivalent) of 0,0-di-nhexyldithiophosphoric acid, 234 grams of mineral oil, 277grams (0.25equivalent) of 40 percent barium petroleum sulfonate and 32 grams (1.0equivalent) of methanol was stirred at 38 C. while being treated with19.1 grams (0.25 equivalent) of barium oxide over a period of tenminutes. The resultant mixture was heated at reflux temperature for 1.5hours, then cooled and treated at 40-55 C. over a 45-minute period withan additional 79.5 grams (1.04 equivalents) of barium oxide while carbondioxide was being bubbled into the mixture. The carbon dioxide treatmentwas continued for 80 minutes after all the barium oxide had been added.The reaction mass was then heated to 150C. and filtered through hyflo.The filtrate was a clear, brown oil, with a slightly sweet odor, andhaving the following analysis:

Barium content, percent 13.7 Neut. No. (acidic) 0.6 Metal ratio 2.9

Example 28 A mixture of 555 grams (0.5 equivalent) of 40 percent bariumpetroleum sulfonate, 87 grams (0.27 equivalent) of 0,0-di-(2-methylpentyl-4) dithiophosphoric acid, 428 grams of mineral oil and 55.5 grams(1.7 equivalents) of methanol was prepared and warmed with agitation to40 C. whereupon 20.3 grams (0.27 equivalent) of barium oxide was added.This mixture was heated with continued agitation at 60-70 C. for anhour, then treated at 40-55 C. with carbon dioxide and an additional 153grams (2.0 equivalents) of barium oxide over a 45 minute period. Thecarbon dioxide treatment was continued for an additional hour, then theproduct mixture was heated to 150 C. and filtered through hyfio. Thefiltrate is a clear, brown oil having the following analyses:

Barium content, percent 13.5

Neut. No. Slightly acidic Metal ratio 3.2

Example 29 A mixture of 209 grams (0.5 equivalent) of 0,0-diisooctyldithiophosphoric acid, 555 grams (0.5 equivalent) of 40 percent bariumpetroleum sulfonate, 197 grams of mineral oil, and 64 grams (2.0equivalents) of methanol was warmed to 35 C., then treated with 38.3grams (0.5 equivalent) of 40 percent barium petroleum sulfonate over a10-minute period. This mixture was heated at reflux temperature for anhour, and simultaneously treated over a 1-hour period at 40 60" C. withcarbon dioxide and an additional 195 grams (2.08 equivalents) of bariumoxide. The carbon dioxide treatment was continued for another minutesand then the product mixture was heated to 150 C. and filtered throughhyfio. The filtrate was a clear, brown oil having a slightly foul odor,and the following analyses:

Barium content, percent 15.0 Neut. No. (acidic) 0.4 Metal ratio 2.5

Example bubbled into the mixture for two hours during which time thetemperature rose from 40C. to 70 C. The resulting mixture was heated to150 C., then filtered through hyfio. The filtrate showed the followinganalyses:

Sulfate ash, percent 27.2

Neut. No. (basic) 3.5

Metal ratio 3.8

Example 31 To a well-stirred mixture of 125 grams (0.5 equivalent) ofnaphthenic acid, 555 grams (0.5 equivalent) of a 40 percent bariumpetroleum sulfonate solution, 144 grams (1.0 equivalent) of nonylalcohol and 125 ml. (4.0 equivalents) of methanol there was addedportion- Wise 268 grams (3.5 equivalents) of barium oxide, whilesimultaneously, carbon dioxide was bubbled into the mixture at a rate of2 cu. ft./hour. The temperature rose to 70 C. during this time and thecarbon dioxide treatment was continued until the mixture was neutral.Then the neutral product was heated to a final temperature of 150 C./ 13mm. and filtered tthrough hyflo. The filtrate was a clear liquid havingthe following analyses:

Sulfate ash, percent 43.1

Neut. No. (basic) 2.5

Metal ratio 3.6

Example 32 Magnesium percent 1.1

Barium percent 7.0

Neut. No. (acidic) 14.7

Metal ratio 2.2

Example 33 Seventy-nine grams (1.04 equivalents) of barium oxide wasadded, at --100 C., to a mixture of 428 grams (0.25 equivalent) of thebarium salt of the phosphorusand sulfur-containing acid of Example 25,277 grams (0.25 equivalent) of 40 percent barium petroleum sulfonate, 98grams 1.0 equivalent) of furfuryl alcohol and 45 grams of water. Themixture was heated to 150 C., and treated at this temperature withcarbon dioxide until it was neutral. The mixture then was heated at 150C./10 mm. and filtered through hyfio. The filtrate was a clear lightbrown, slightly viscous liquid having the following analyses:

Barium percent 12.0 Neut. No. Slightly acid Metal ratio 3.0

Example 34 To a mixture of 1140 grams (1.0 equivalent) of 40 percentbarium petroleum sulfonate, 196 grams (2.0 equivalent) of furfurylalcohol, 52 grams of mineral oil and 75 grams of water, there was added,at SO-100 C., 168 grams (4.0 equivalents) of lithium hydroxidernOnohydrate, The resulting mixture was heated to C. and treated for onehour with carbon dioxide, The neutralized mixture was filtered throughhyfio, yielding as filtrate a 17 clear, dark brown, slightly viscousliquid having the following analyses:

Example 35 Five equivalents (392 grams) of barium oxide was addedportionwise over a period of 45 minutes to a wellstirred mixture of 1638grams (1.25 equivalents) of lead petroleum sulfonate, 245 grams (2.5equivalents) of furfuryl alcohol, and 625 grams of mineral oil heated at85-130 C. Carbon dioxide was bubbled into the mixture throughout thisperiod and additionally until the mixture was neutral. The neutralmixture was concentrated by heating to a final temperature of 150 C./30mm., and the residue filtered through hyfio. The filtrate was a slightlyviscous, clear, brown liquid having the following analyses:

Example 36 A mixture of 574 grams (0.5 equivalent) of 40 percent bariumpetroleum sul-fonate, 98 grams (1.0 equivalent) of furfuryl alcohol, and762 grams of mineral oil was heated with stirring at 100 C. for an hour,then treated portionwise over a 15-minute period with 230 grams (3.0equivalents) of barium oxide. During this latter period the temperaturerose to 120 C. (because of the exothermic nature of the reaction ofbarium oxide and the alcohol); the mixture then was heated at 150- 160C. for an hour, and treated subsequently at this temperature for 1.5hours with carbon dioxide. The material was concentrated by heating to afinal temperature of 150 C./ mm. then filtered through hyflo to yield aclear, oil-soluble filtrate having the following analyses:

To a stirred mixture of 250 grams (1.0 equivalent) of naphthenic acid,102 grams (1.0 equivalent) of furfuryl alcohol, and 1228 grams ofmineral oil there was added 83 grams (1.1 equivalents) of barium oxide.This mixture was heated to .120 C. and treated portionwise over a periodof one hour with an additional 300 grams (3.9 equivalents) of bariumoxide. Carbon dioxide was bubbled into the mixture throughout this hour,during which the temperature rose to 150 C. This temperature wasmaintained for an additional hour whereupon the mixture was concentratedby heating to a final temperature of 160 C./ 10 mm. The hot residue wasfiltered through hyfio to yield a clear, brown, oil-soluble liquidhaving the following analyses:

Sulfate ash percent 23.0

Neut. No. (basic) 1.7 Metal ratio 3.6

Example 38 To 1000 grams (7.7 moles) of 2-ethylhexanol there was addedwith stirring over a period of one hour 100 grams (0.73 mole) of freshlycut barium. This mixture then was heated at 150 C. with continuedstirring for two hours, at which point all of the solid barium haddisappeared. The solution was filtered.

and a clear, brown, slightly viscous filtrate was obtained which had thefollowing analyses:

Sulfate ash percent 24.9

Neut. No. (basic) 0.8

Metal ratio 3.1

Example 39 To a solution of 5 34 grams (0.44 equivalent) of a basicbarium petroleum sulfonate having a metal ratio of 2.2 in 133 grams ofmineral oil there was added with stirring at -60-70 C. 1000 grams (1.26equivalents) of a barium alcoholate solution prepared as in Example 38.The resulting mixture was heated at this temperature for an hour, thentreated at C. with carbon dioxide for an hour. The product wasconcentrated by heating to a final temperature of C./2 mm., and theresidue was filtered through hyflo. The filtrate was a clear, brown,non-viscous liquid which showed the following analyses:

Sulfate ash, percent 28.9

Neut. No. Slightly aci Metal ratio 4.7

Example 40 To 800 grams of methanol there was added portionwise withstirring at room temperature 306 grams (4.0 equivalents) of bariumoxide, and the resulting mixture was stirred at reflux temperature foran hour. The product mixture was filtered and the filtrate wasconcentrated by heating to 40 C./ 15 mm. The residue was a white solidwhich weighed 376 grams.

A mixture of 188 grams (1.84 equivalents) of the above product, 582grams (0.45 equivalent) of 40 percent barium petroleum sulfonate, and 45grams of methanol was stirred at 60-70 C; for 30 minutes, then treatedat 6070 C. with carbon dioxide for three hours; the resulting productwas heated to 15 0 C. and filtered through hyflo. The filtrate was aclear, brown oil having the following analyses:

Sulfate ash, percent 31.1

Neut. No. Slightly acid Metal ratio 4.5

Example 41 To 2000 ml. of methanol at reflux temperature there was addedportionwise 120 grams (10 equivalents) of magnesium. The resultingsolution was treated with 735 grams of mineral oil and 1216 grams (2.0equivalents) of petroleum sulfonic acid and then heated at refluxtemperature for an hour. Methanol was removed by distillation, leaving aviscous residue to which was added with stirring at 80 C. over a periodof 20 minutes, 72 grams (8 equivalents) of water. The resulting clear,brown product had the following analyses:

Sulfate ash, percent 19.5 Neut. No. (basic) 102.2 Metal ratio 4.8

This product was warmed to 80 C. and treated with carbon dioxide forfive hours at which point further carbon dioxide treatment failed toreduce the neut. No. of 9.0.

1 9 Example 42 Barium methylate was prepared by adding 206 grams (3.0equivalents) of barium to 300 grams of well-stirred methanol. Thetemperature rose from 24 to 75 C. and stirring was continued at thisreflux temperature for two hours. The mixture was concentrated byheating to 70 C./ mm. leaving a white solid residue apparently free ofunchanged barium.

To this white solid (barium methylate) there was added 100 grams ofmethanol, 1148 grams (1.0 equivalent) of 40 percent barium petroleumsulfonate and 16 grams of mineral oil, and the whole was heated withstirring at 72 C. for an hour. The resulting clear solution was dividedinto two equal portions, A and B which were treated as follows:

A. The one portion was treated with carbon dioxide at 72-75 C. until(2.5 hours) slightly acidic as indicated by phenolphthalein. It was thenconcentrated by heating to 150 C., and 435 grams of mineral oil wasadded. The fluid mixture was filtered and the brown filtrate shown tohave the following:

Sulfate ash, percent 17.4 Neut. No. (acidic) 2.0 Metal ratio 3.5

Sulfate ash, percent 22.6

Neut. No. (acidic) 8.6

Metal ratio 3.5

Example 43 A 40 percent solution of barium petroleum sulfonate inmineral oil, weighing 574 grams (0.5 equivalent), was heated to 150 C.and diluted with 238 grams of mineral oil and then treated with 90 grams(1.0 equivalent) of ethyl Cellosolve. To this mixture, now at 110 C.,there was added 153 grams (2.0 equivalents) of barium oxide and theresulting mass was heated with stirring at 150- 160 C. for an hour. Thencarbon dioxide was bubbled into the mixture at ISO-160 C. for an hour.This temperature was maintained for an additional hour prior tofiltering the mass through hyflo. The filtrate was a clear, brown, fluidmass having the following analyses:

To 574 grams (0.5 equivalent) of a 40 percent barium petroleum sulfonatesolution in mineral oil, at 150 0, there was added an additional 238grams of mineral oil. At this point the temperature had receded to 115C. and 61 grams (2.0 equivalents) of ethanol-amine was added; then 153grams (2.0 equivalents) of barium oxide was added and the resultingmixture was heated at ISO-160 C. for an hour. Carbon dioxide was bubbledinto the mass at 150--160 C. for an hour, after which this temperaturewas maintained for an additional hour. The mixture was filtered throughhyflo to yield a light brown, fluid filtrate having the followinganalyses:

Sulfate ash, percent 24.5 Neut. No. (acidic) 5.4 Metal ratio 4.3

20 Example 45 To 1900 grams (2.3 equivalents) of an oil solution of a SO-50 mixture of sodium petroleum sulfonate and sodium didodecyl benzeneat C. there was added 142 grams (1.28 equivalents) of calcium chloridein 200 grams of water. This mixture was heated for an additional twohours at 95 C. whereupon 148 grams (4.0 equivalents) of calciumhydroxide was added. This mixture was heated for 5 hours at 150 C. andthen blown with nitrogen at this temperature for 30 minutes to removethe water. The mixture was allowed to cool to 35 C. and then 500 gramsof methanol was added. This mixture was treated with carbon dioxideuntil the neut. No. of the mixture was 0.7 (basic). The product wasdiluted with an additional 230 grams of oil and then freed of methanolby distillation. The product was filtered through a siliceous filteraid, the filtrate showing the following:

Example 46 A mixture of 1,305 grams (1.3 equivalents) of a carbonatedbasic calcium sulfonate having a metal ratio of 2.5 (prepared by thereaction of a sodium petroleum sulfonate with calcium chloride andcalcium hydroxide), 930 grams of mineral oil, 220 grams of methanol, 72grams of isobutyl alcohol and 38 grams of amyl alcohol was prepared,heated to 35 C. and subjected to the following operating cycle 4 times:

Add 143 grams of 90% calcium hydroxide and treat with carbon dioxideuntil the mixture has a base No. of 32-39.

The product is then heated to C. during a period of nine hours to removethe alcohols, and then filtered through a silicone filter aid at thissame temperature. The filtrate has the following analyses:

A mixture of 300 grams of mineral oil, 99 grams (0.76 equivalent) ofoctyl alcohol, 2.57 grams (3.36 equivalents) of barium oxide, 234 grams(0.81 equivalent) of oleic acid, and 45 grams (5 equivalents) of wateris heated with stirring to reflux temperature in about 1 hour. Themixture then is heated to a temperature of 135 145 C., and maintained atthis temperature for a period of about 0.5 hour. This mixture is treatedwith C0 (2 cubic ft. per hour) at 145 C. for a period of about 2 hours.The resulting mixture is heated to C. and filtered. The filtrate has thefollowing analyses:

Sulfate ash (percent) 34.5

Metal ratio 2.9

Neut. No. (acidic) 0.4

Example 48 21 of about 1.5 hours and then heated to 190 C. and filtered.The filtrate has the following analyses:

Sulfate ash (percent) 26.87 Metal ratio 3.1 Neut. No. (acidic) 0.3

Example 49 A mixture of 2576 grams of mineral oil, 240 grams (1.85equivalents) of octyl alcohol, 740 grams (20.0 equivalents) of calciumhydroxide, 2304 grams (8 equivalents) of oleic acid, and 392 grams (12.3equivalents) of methyl alcohol is heated with stirring to a temperatureabout 50 C. in about 0.5 hour. This mixture then is treated with C (3cubic ft. per hour) at 50-60 C. for a period of about 3.5 hours. Theresulting mixture is heated to 150 C. and filtered. The filtrate has thefollowing analyses:

Sulfate ash (percent) 24.1 Metal ratio 2.5 Neut. No. (acidic) 2.0

Example 50 A mixture of 932 grams of mineral oil, 100 grams (0.77equivalent) of octyl alcohol, 370 grams (10.0 equivalents) of calciumhydroxide, 287 grams (1.0 equivalent) of oleic acid, and 150 grams (4.6equivalents) of methyl alcohol is heated with stirring to a temperatureof about 55 C. in about 0.5 hour. This mixture then is treated with C0(2 cubic ft. per hour) at 55 C. for a period of about 6 hours. Theresulting mixture is heated to 150 C. and filtered. The filtrate has thefollowing analyses:

Sulfate ash (percent) 30.6 Metal ratio 7.5 Neut. No. (basic) 3.0

Example 51 A relatively high molecular weight carboxylic acid isobtained by reacting a chlorinated polyisobutene having a molecularweight of 1000 and a chlorine content of 4.5% with acrylic acid. Amixture of the above-prepared carboxylic acid (982 grams, 1 equivalent),mineral oil (1368 grams), water (50 grams), 50% aqueous calclum chloridesolution (15 grams) is heated to 80 C. and mixed with calcium hydroxide(296 grams). The mixture is then heated at 100 C. for one hour and thendried by heating it to 160 C. while it is blown with nitrogen. To theresidue at 60 C. there are added isooctyl alcohol (272 grams) and methylalcohol (296 grams) and the resulting mixture is blown with carbondioxide at 50- 55 C. until it has a base number of 23. The residue isthen dried at 150 C. in nitrogen atmosphere and filtered. The filtrateis found to have the following analyses:

(A) an oil soluble acyclic carboxylic acid having at least about 12carbon atoms or the metal salt thereof; (B) a basically reacting alkalior alkaline earth metal 22 compound from which the metal cation isliberated when contacted with an acidic material having an ionizationconstant greater than 1.5)(10' in Water at 25 C. and present in anamount such that there is present in the mass substantially more than 2equivalents of metal per equivalent of (A);

(C) at least 0.1 equivalent of an alcohol per equivalent of (B); andreacting under substantially anhydrous conditions the mass with aninorganic acidic material having an ionization constant higher than thatof the alcohol of (C).

2. The process of claim 1 wherein the acyclic carboxylic acid of (A) isa fatty acid having from about 12 to about 30 carbon atoms.

3. The process of claim 1 wherein the acyclic carboxylic acid of (A) isan unsaturated fatty acid having from about 12 to about 30 carbon atoms.

4. The process of claim 1 wherein the basically reacting metal compoundof (B) is an alkaline earth metal base selected from the classconsisting of oxides, hydroxides, and alcoholates.

5. The process of claim 4 wherein the metal of the alkaline earth metalbase is calcium or barium.

6. The process of claim 1 wherein the alcohol of (C) is an alkanolhaving up to about 30 carbon atoms.

7. The process of claim 1 wherein the inorganic acidic material iscarbon dioxide.

8. A process which comprises preparing a mass consisting of (A) anoil-soluble fatty acid having from about 12 to about 30 carbon atoms ora calcium or barium salt thereof; (B) a calcium or "barium base selectedfrom the class consisting of oxides, hydroxides, and alcoholates and (C)an alkanol having up to about 30 carbon atoms; and reacting undersubstantially anhydrous conditions the mass with carbon dioxide.

9. The process which comprises preparing a mass consisting essentiallyof (A) oleic acid or barium oleate; (B) barium hydroxide; and (C) alower alkanol; and reacting under substantially anhydrous conditions themass with carbon dioxide.

10. A process for preparing an oil-soluble highly basic metal salt of anorganic acid, said process comprising reacting under substantiallyanhydrous conditions an oilsoluble organic acid compound selected fromthe class consisting of acyclic carboxylic acids and alkali and alkalineearth metal salts thereof, in the presence of at least 5% of the weightof said organic acid compound of a lower alkanol, with an alkaline earthmetal carbonate formed in situ by the reaction of carbon dioxide and analkaline earth metal base in an amount such that there is present in thereaction mass substantially more than two equivalents of the metal baseper equivalent of the organic acid compound, thereafter removing saidalkanol and any water present in the resulting mixture.

11. The process of claim 10 wherein the organic acid compound is a fattyacid having from about 12 to about 30 carbon atoms.

12. The process of claim 10 wherein the alkaline earth metal base is acalcium or barium base selected from the class consisting of oxides,hydroxides, and alcoholates.

13. A process for preparing an oil-soluble highly basic metal salt offatty acid, said process comprising reacting under substantiallyanhydrous conditions a fatty acid having from about 12 to about 30carbon atoms or an alkaline earth metal salt thereof, in the presence ofat least about 5% of the weight of said acid or the metal salt thereofof a lower alkanol, with an alkaline earth metal carbonate formed insitu by the reaction of carbon dioxide and an alkaline earth metal baseselected from the class consisting of oxides, hydroxides, andalcoholates in an amount such that there is present in the reaction masssubstantially more than two equivalents of the metal base per equivalentof the acid or the metal salt thereof, thereafter removing said alkanoland any water present in the resulting mixture.

' 14. The process of claim 13 wherein the alkaline earth metal base is acalcium or a barium 'base.

References Cited UNITED STATES PATENTS FOREIGN PATENTS 786,167 11/1957Great Britain.

PATRICK P. GARVIN, Primary Examiner 5 I. VAUGHN, Assistant ExaminerAsseff et a1. 252--39 XR Asseff et a1. 2S239 XR U S C1. X R.

gifi f i ftj iii 44 70; 106310; 25218, 41, 389, 352; 260-18, AndfeSS252-39 XR 10 5, 1

Carlyle et a1. 2S239 XR Le Suer et a1. 25233

